DE19632913A1 - Cosmetic and dermatological sunscreen formulations containing triazine derivatives and glycerol mono- or dicarboxylic monoesters - Google Patents

Description

The present invention relates to cosmetic and dermatological light protection especially skincare cosmetic and dermatological sunscreen preparations.

The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength smaller than 290 nm (the so-called UVC range), absorbed by the ozone layer in the earth's atmosphere be, cause rays in the range between 290 nm and 320 nm, the soge called UVB, erythema, simple sunburn or even more or less severe burns.

As a maximum of the erythema efficiency of sunlight becomes the narrower area indicated at 308 nm.

To protect against UVB radiation, numerous compounds are known in which It is mostly derivatives of 3-Benzylidencamphers, the 4-aminobenzoic acid, the Cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole is.

Also for the range between about 320 nm and about 400 nm, the so-called UVA Area, it is important to have filter substances available as well Radiation can cause damage. So it is proven that UVA radiation to a Damage to the elastic and collagen fibers of the connective tissue leads to what the Skin ages prematurely, and that they are the cause of numerous phototoxic and pho  allergic reactions can be seen. The damaging influence of UVB radiation can be amplified by UVA radiation.

The UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with the skin metabolism.

Predominantly, such photochemical reaction products are radi kalische connections, z. B. hydroxyl radicals. Also undefined radical Photopro Due to their high reactivity, unreacted substances which are formed in the skin itself controlled controlled reactions to the day. But also singlet oxygen, a Non-radical excited state of the oxygen molecule can under UV irradiation occur, as are short-lived epoxides and many others. Singlet oxygen, for example is distinguished from the normally existing triplet oxygen (radi alkaline ground state) due to increased reactivity. However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

Furthermore, UV radiation counts as ionizing radiation. So there is a risk that also arise ionic species on UV exposure, which in turn oxidative in to be able to intervene in the biochemical processes.

An advantageous UVB filter is 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoate acid tris (2-ethylhexyl ester), synonym: 2,4,6-tris [anilino (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine.

This UVB filter substance is sold by BASF Aktiengesellschaft under Warenbe UVINUL® T 150 is sold and is characterized by good UV absorption properties.

The main disadvantage of this UVB filter is the poor solubility in lipids. Known Solvents for this UVB filter can release a maximum of about 15% by weight of this filter corresponding to about 1-1.5 wt .-% dissolved, and thus active, UV filter substance.

It was, however, surprising and for the expert not foresee that light protective active ingredient combinations

• (a) 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester) and
• (B) one or more surfactants selected from Group of glycerol mono- or dicarboxylic monoesters of the general formula

where R₃ represents a branched or unbranched acyl radical having 6-24 carbon atoms,
to remedy the disadvantages of the prior art

In particular, according to the invention, the use of one or more surfactants selected from the group of glycerol mono or dicarboxylic acid monoester of the general formula

wherein R₃ is a branched or unbranched acyl radical having 6-24 carbon atoms represents, as a solvent, solubilizer or solubilizer for 4,4 ', 4' '- (1,3,5-tria zin-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), especially for the Ver use in sunscreens.  

It is possible according to the invention the amounts of 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyl triimino) tris-benzoic acid tris (2-ethylhexyl ester) in cosmetic or dermatological Preparations over the prior art to double.

It was surprising that by adding inventively used grenzflächenakti ver glycerol mono- or dicarboxylic monoester a stabilization of solutions of 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester) be acts because the latter substance not only has poor solubility, but also easily crystallized from its solution again. Therefore, according to the invention also a method of stabilizing solutions of the 4,4 ', 4 "- (1,3,5-tazin-2,4,6-triyltrimi no) tris-benzoic acid tris (2-ethylhexyl ester), characterized in that such Lö an effective content of glycerol mono- or dicarboxylic acid monoesters is added.

R₃ is preferably a myristyl radical, palmityl radical, stearyl radical or eicosyl radical.

Particularly advantageous in the sense of the present invention has proven to be under Point (b) listed surface-active substances the glyceryl stearate ago issued, which is commercially available, for example, under the trade name Tegin® M is available from Th.Goldschmidt KG.

The total amount of 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2- ethylhexyl ester) in the finished cosmetic or dermatological preparations is advantageously from the range of 0.1-10.0 wt .-%, preferably 0.5-6.0 wt .-% chosen, based on the total weight of the preparations.

The total amount of one or more grenzflä used in the invention chenaktiven glycerol mono- or dicarboxylic monoesters in the finished kosmeti or dermatological preparations is advantageously from the range of 0.1- 25.0% by weight, preferably 0.5-15.0% by weight, based on the total weight the preparations.

It is advantageous to use weight ratios of 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino) -tris- benzoic acid tris (2-ethylhexyl ester) and one or more inventively ver  used glycerol mono- or dicarboxylic acid monoesters in the range of 1:10 to 10: 1, preferably 1: 4 to 4: 1, to choose.

Cosmetic and dermatological preparations according to the invention contain advantage In addition, inorganic pigments based on metal oxides and / or other in Water sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO₂), zinc (ZnO), iron (eg Fe₂O₃), zirconium (ZrO₂), silicon (SiO₂), Manganese (eg MnO), aluminum (Al₂O₃), cerium (eg Ce₂O₃), mixed oxides of the corre ing metals and mixtures of such oxides. Particularly preferred han these are pigments based on TiO₂.

It is particularly advantageous in the context of the present invention, although not zwin when the inorganic pigments are in hydrophobic form, d. h. that she are superficially treated water-repellent. This surface treatment can consist in that the pigments according to known methods with a thin be provided hydrophobic layer.

One such method is, for example, that the hydrophobic surfaces according to a reaction according to

n TiO₂ + m (RO) ₃Si-R '→ n TiO₂ (surface)

is produced. n and m are random stoichiometric parameters meter, R and R 'are the desired organic radicals. For example, in analogy to DE OS 33 14 742 illustrated hydrophobized pigments are advantageous.

Advantageous TiO₂ pigments are, for example, under the trade names MT 100 T from TAYCA, M 160 from Kemira and T 805 from Company Degussa available.

The cosmetic and / or dermatological sunscreen formulation according to the invention ments may be composed as usual and the cosmetic and / or the Photological light protection, furthermore for the treatment, care and cleaning of the Skin and / or hair and serve as a make-up product in decorative cosmetics.  

For use, the cosmetic and dermatological according to the invention Preparations in the usual way for cosmetics on the skin and / or hair in applied sufficient amount.

Particularly preferred are such cosmetic and dermatological preparations, which are in the form of a sunscreen. Advantageously, these can additionally at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micro pigment, included.

The cosmetic and dermatological preparations according to the invention can contain cosmetic excipients, as ver usually in such preparations ver be used, for. As preservatives, bactericides, perfumes, substances for Ver foaming, dyes, pigments having a coloring effect, Ver thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation Such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic Solvent or silicone derivatives.

An additional content of antioxidants is generally preferred. Erfindungsge As favorable antioxidants, they can all be used for cosmetic and / or dermatological purposes Applications of suitable or common antioxidants can be used.

Advantageously, the antioxidants are selected from the group consisting of amino acid ren (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg Uro caninsäure) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives vate (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg. Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, Methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, choles steryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipro Pionat, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, Nukleoti de, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in very  low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg, α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, Bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and de ren derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, Furfurylidene sorbitol and its derivatives, ubiquinone and ubiquinol and their derivatives, Vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), Tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α- Glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhy droxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyro phenone, uric acid and its derivatives, mannose and its derivatives, zinc and its Derivatives (eg ZnO, ZnSO₄) selenium and its derivatives (eg selenomethionine), stilbenes and their derivatives (eg, stilbene oxide, trans-stilbene oxide) and the present invention ge suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and Lipids) of these drugs.

The amount of the aforementioned antioxidants (one or more compounds) in the Preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 wt .-%, in particular 1-10 wt .-%, based on the total weight of Zuberei tung.

If vitamin E and / or its derivatives are the antioxidant (s) advantageous, their respective concentrations in the range of 0.001-10 wt .-%, based on the total weight of the formulation to choose.

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives, the or which are antioxidants is advantageous, their respective concentrations from the Range of 0.001-10% by weight based on the total weight of the formulation choose.

The lipid phase can advantageously be selected from the following substance group:

• - mineral oils, mineral waxes
• - Oils, such as triglycerides of capric or caprylic acid, but preferably Rizi nusöl;  
• - Fats, waxes and other natural and synthetic fats, preferably Esters of fatty acids with lower C-number alcohols, e.g. B. with isopropanol, propy glycol or glycerol, or esters of fatty alcohols with lower alkanoic acids C number or with fatty acids;
• - alkyl benzoates;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions For the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched Alkancar bonsäuren a chain length of 3 to 30 carbon atoms and saturated and / or unsatd saturated, branched and / or unbranched alcohols of a chain length of 3 to 30 C Atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then be chosen advantageously from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n- Butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl iso nonanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, and synthetic, semysin thetic and natural mixtures of such esters, e.g. B. jojoba oil.

Furthermore, the oil phase can be advantageously selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols le, as well as the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length ge from 8 to 24, in particular 12-18 C-atoms. The fatty acid triglycerides may be included For example, be advantageously selected from the group of synthetic, semisyntheti and natural oils, eg. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, Almond oil, palm oil, coconut oil, palm kernel oil, and the like.

Any mixtures of such oil and wax components are advantageous in Use of the present invention. It may also be advantageous if necessary  waxes, for example cetyl palmitate, as the sole lipid component of the oil phase use.

Advantageously, the oil phase is selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Particularly advantageous are mixtures of C _12-15 -alkyl benzoate and 2-Ethylhexylisostea rat, mixtures of C _12-15 -alkyl benzoate and Isotridecylisononanoat and mixtures of C _12-15 -alkyl benzoate, 2-Ethylhexylisostearat and Isotridecylisononanoat.

Of the hydrocarbons, paraffin oil, squalane and squalene are advantageous in the sense to use the present invention.

Advantageously, the oil phase may further contain cyclic or linear silicone oils or consist entirely of such oils, although it is preferred that in addition to the silicone oil or the silicone oils an additional content of other oil phase vertical components to use.

Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the invention used silicone oil. But other silicone oils are beneficial in Sin ne of the present invention, for example hexamethylcyclotrisiloxane, Polydimethylsiloxane, poly (methylphenylsiloxane).

Also particularly advantageous are mixtures of cyclomethicone and isotridecylisono nanoate, from cyclomethicone and 2-ethylhexyl isostearate.

The aqueous phase of the preparations according to the invention optionally contains geous

• - Alcohols, diols or polyols low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol mo noethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl- or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous Products, also low C-number alcohols, e.g. For example, ethanol, isopropanol, 1,2-Pro pandiol, glycerol and in particular one or more thickening agents, wel  Ches or which can be advantageously selected from the group silicon di oxide, aluminum silicates, polysaccharides or their derivatives, for. Hyaluronic acid, Xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the Group of polyacrylates, preferably a polyacrylate from the group of soge named Carbopols, for example Carbopols of types 980, 981, 1382, 2984, 5984, each individually or in combination.

The cosmetic or dermatological sunscreen preparations contain advantageous inorganic pigments, in particular micropigments, for. B. in amounts of 0.1 wt .-% to 30 wt .-%, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular but 1 wt .-% to 6 wt .-%, based on the total weight of the preparations.

It is advantageous according to the invention, in addition to the combinations according to the invention öllös Liche UVA filters and / or UVB filters in the lipid phase and / or water-soluble UVA Use filters and / or UVB filters in the aqueous phase.

Advantageously, the sunscreen formulations according to the invention can be further substituents containing UV radiation in the UVB range, the total amount the filter substances z. 0.1% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6 wt .-%, based on the total weight of the preparation to provide cosmetic preparations that protect the skin from the skin protect entire area of ultraviolet radiation. They can also be called suns serve as a protective agent.

The other UVB filters may be oil-soluble or water-soluble. Advantageous oil-soluble UVB filter substances are z. B .:

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3 benzylidenecamphor;
• 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2- ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4- methoxycinnamate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;  
• Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhe xyl ester);

Advantageous water-soluble UVB filter substances are z. B .:

• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or tri ethanolammonium salt, as well as the sulfonic acid itself;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzene zophenone-5-sulfonic acid and its salts;
• - Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bornylidenme thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and their Salts.

The list of said other UVB filters used in combination with the erfindungsge Of course, active ingredient combinations can be used, of course not be limiting.

It may also be advantageous to use the combinations according to the invention with others To combine UVA filters, which have traditionally been used in cosmetic preparations are included. These substances are preferably derivatives of Dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) pro pan-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. Also this comm combinations or preparations containing these combinations are subject matter the invention. The quantities used for the UVB combination can be used become.

Furthermore, it is advantageous to combine the active substance combinations according to the invention with further UVA and / or UVB filters.

It is also particularly advantageous to use the active compound combinations according to the invention Salicylic acid derivatives, some of which are known, which can also absorb UV radiation. To common UV filters belong

The invention also provides a process for the preparation of the novel process cosmetic and / or dermatological sunscreens characterized in that in a conventional manner the 4,4 ', 4' '- (1,3,5-triazine) 2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) in one or more of the same According to used surface-active glucose derivatives or an oil phase containing a surface-active glucose surfactant used in accordance with the invention with uniform stirring and optionally with heating and suspended if desired homogenized, optionally with further lipid components and optionally combined with one or more emulsifiers, then the oil phase with the aqueous phase, in which optionally incorporated a thickener and which preferably has about the same temperature as the oil phase, mixed, homogenized if desired and cooled to room temperature leaves. After cooling to room temperature, especially when still volatile Be be incorporated into the components, re-homogenizing done.

The following examples are intended to illustrate the present invention without it limit. All quantities, percentages and percentages are, if not otherwise indicated, on the weight and the total amount or on the total amount weight of the preparations.

example 1

Wt .-% Glyceryl stearate SE 3.50 sorbitan 1.80 glycerin 3.00 cetearyl 0.50 octyldodecanol 7.00 Caprylylether 8.00 Uvinul T150 3.00 cetearyl 6.00 Carbomer 0.20 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Example 2

Wt .-% glyceryl stearate 2.50 sorbitan 3.50 glycerin 3.00 Cetearyl alcohol 1.50 Sodium hydroxide 45% 0.13 octyldodecanol 7.00 Capric / Caprylic triglycerides 5.00 Cetearyl isononanoate 6.00 Uvinul T150 5.00 Carbomer 0.20 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Example 3

Wt .-% sorbitan 3.50 butylene 5.00 Cetearyl alcohol 3.00 Xanthan gum 0.35 C12-C15 alkyl benzoates 10.00 Uvinul T150 4.00 Cetearyl Isononanoate 6.00 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Example 4

Wt .-% Glyceryl stearate SE 3.50 sorbitan 1.80 glycerin 3.00 cetearyl 0.50 octyldodecanol 7.00 Caprylylether 8.00 Uvinul T150 3.00 Parsol 1789 2.00 Eusolex 6300 1.00 Titanium dioxide 2.00 cetearyl 6.00 Carbomer 0.20 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Example 5

Wt .-% glyceryl stearate 2.50 sorbitan 3.50 glycerin 3.00 Cetearyl alcohol 1.50 Sodium hydroxide 45% 0.13 octyldodecanol 7.00 Capric / Caprylic triglycerides 5.00 Cetearyl isononanoate 6.00 Uvinul T150 5.00 Parsol 1789 2.00 Eusolex 6300 1.00 Titanium dioxide 2.00 Carbomer 0.20 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Example 6

Wt .-% sorbitan 3.50 butylene 5.00 Cetearyl alcohol 3.00 Xanthan gum 0.35 C12-C15 alkyl benzoates 10.00 Uvinul T150 4.00 Parsol 1789 2.00 Eusolex 6300 1.00 Titanium dioxide 2.00 Cetearyl Isononanoate 6.00 preservative q.s. Perfume q.s. Water, demin. ad 100.00

Claims (4)

1. Sunscreen effective drug combinations

• (a) 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester) and
• (B) one or more surfactants selected from the group of glycerol mono- or dicarboxylic monoesters of the general formula wherein R₃ represents a branched or unbranched acyl radical having 6-24 carbon atoms.

2. Use of one or more surface-active substances selected from the group of glycerol mono- or dicarboxylic monoesters of the general formula wherein R₃ represents a branched or unbranched acyl radical having 6-24 carbon atoms, as a solvent or solubilizer or solubilizer for 4,4,4 '' - (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), in particular for use in light stabilizers. 3. Combinations according to claim 1 or use according to claim 2, characterized ge indicates that the total amount of 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino) -tris- benzoic acid tris (2-ethylhexyl ester) in the finished cosmetic or dermatological Preparations in the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight is selected, in each case based on the total weight of the preparations. 4. Combinations according to claim 1 or use according to claim 2, characterized ge indicates that the total amount of glycerol mono- or dicarboxylic acid mono  esters, in the finished cosmetic or dermatological preparations from the Range of 0.1-25.0 wt .-%, preferably 0.5-15.0 wt .-% is selected, each be based on the total weight of the preparations.